DE2123772A1 - - Google Patents

Description

PATENT LAWYERS MUNICH 15
KAISER-LUDWIG-PLATZ 6
TEL. 0811/530211
530212
CABLES: THOPATENT
TELEX: TO FOLLOW Dipi.-chem. Dr. D- Thomsen Dipi.-mg. H. Tiedtke
Dipl.-Chem. G. BÜtlSlitg Dipl.-Ing. R. ΚίηΠΘ FRANKFURT (MAIN) 50
FUCHSHOHL 71
TEL. 0811/514688 ■ DipL-ing. W. Wein ka uff 2123772

Reply requested to: Please reply to:

8000 Munich 15 ^{l3 May 1971}

UNIROYAL, Inc.

New York 10020 (USA)

Composition for producing a dry cleanable sheet material from artificial leather as well as other uses

The invention relates to a composition which consists of a mixture of (A) thermoplastic polyurethane elastomer with (3) vinyl chloride-vinyl acetate-vinyl alcohol copolymer resin or contains such a mixture.

Thermoplastic polyurethane elastomer, as it is according to the invention is used is a conventional material (see for example "Polyurethane Technology" from Bruins, Interscience Publishers, pages 19 8 to 200, and "Modem Plastics Encyclopedia", 1968, page 289). examples are Polyether-based polyurethane like the one made from

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2 moles of polytetramethylene ether glycol, 2 moles of MDl and 1 mole of 1,4-butanediol is prepared, as well as polyurethanes based on polyester, such as those derived in a similar manner from 1,4-butanediol-aipic acid polyester and MDI (Rubber Chemistry ana Technology, Volume 35, 1962 , Page 742, Schollenberger et al). ί, η Commercially available materials of this type include Estane 5701 or 5640X071 or Royalar A-850. Many such products can be described as reaction products of a polymeric polyol (e.g. a polyester glycol or a polyether glycol) with an organic polyisocyanate, usually a diisocyanate, often together with a low molecular weight bifunctional substance which has two reactive hydrogens such as a glycol or di ' ainin (see U.S. Patent 3,462,326, particularly column 3, lines 1 to 35).

The vinyl chloride-vinyl acetate-vinyl alcohol copolymer used in the composition of the invention is also a known substance (described in "Polyvinyl Chloride" by Sarvetnick, page 24, produced by hydrolysis of Acetate groups in vinyl chloride-acetate copolymers). It is referred to as a "crosslinking vinyl", with the ability to crosslink is a consequence of the presence of hydroxyl groups.

The ratio of the polyurethane elastomer to the vinyl resin described can be varied to achieve optimum

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physical properties in special laminates or to create special layers of laminates. Included Mixtures according to the invention 30 to 90 parts, preferably 40 to 85 parts of the polyurethane (A) and 10 to 70 parts, preferably 15 to 60 parts of the vinyl resin described (B) per 100 parts by weight of polyurethane plus vinyl resin. The addition of vinyl resin to the urethane gives good flexibility and unc Toughness, but at very low levels some unsuitability for some surface applications because of one remaining sticking. Therefore, the compound contains for use as a slip coating or as a liaut coating when forming the outer Layer of an object, which according to one embodiment of the invention, usually larger amounts of vinyl resin, resulting in a fairly hard, dry, wear-resistant Coating ces patent leather type leads which Suitable for footwear or other purposes where a senr / calibrated structure is not required. So can Glossy preparations for covering skin of footwear to 35 to 65 parts, preferably 40 to 55 parts of urethane (A) and 35 to 65 parts, preferably 45 to 60 parts Form vinyl resin (B) for every 100 parts by weight of (A) plus (B). Support covers or pads that contain less vinyl resin result in a very flexible, somewhat tacky Layer with good layering properties. Base or layering layer preparations can therefore affect 70 to 80 parts, preferably 75 to 85 parts of polyurethane

(A) and 10 to 25, preferably 15 to 25 parts of vinyl resin

(B) per 100 parts by weight of (A) plus (B), with those

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Preparations with little vinyl resin also for the formation of building coatings or sliding coatings are adaptable where high flexibility, a soft structure and good draping properties are required such as various items of clothing.

In another embodiment, the invention comprises the incorporation of an amino resin, especially one Melamine resin, and in particular an etherified melamine resin in the crowd. The known substance hexakis (raethoxymethyl) melamine is suitable for this purpose, which the commercially available Piarz is known as the Cymel (Modem Plastics Encyclopedia, 1968, p. 156). Only a small amount of this resin, for example 0.5 to 10 parts, preferably 1 to 7 parts per 100 parts by weight of urethane (A) plus vinyl resin (B) needs to be used. To a or several layers of the laminate belong to a mixture, which contains the melamine resin for optimal resistance to give to dry cleaning.

The composition of the present invention can be formed into a film, sheet or coating by any suitable conventional method. A particularly suitable way is that they are the mass in a conventional inert organic solvent or solvent mixture dissolves _x in which the components soluble. The solution can be applied to a surface in a suitable, conventional manner, for example by

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painting, spreading, coating or spraying on which it is desired to form the film or sheet, after which the solvent is allowed to evaporate, a continuous deposition remaining, which results from the inventive Mass is composed. The removal of the solvent is facilitated by heating, for example by Infrared heater or in an oven, and such heating also serves to cure the coating. Even if the invention should not be restricted to a particular theory of work, it is assumed that as a result of the heating the mass is networked. It is believed that the melamine resin described can exert a hardening effect possibly by reaction with hydroxyl groups in the vinyl copolymer. Anyway, it increases the toughness of the The bulk and solubility of the vinyl resin is reduced, thereby increasing the dry cleanability of the product will.

The material can be deposited from solution onto a temporary pouring or releasing surface which does not form part of the finished product, or it can be deposited on a surface which is intended to a coherent part of the finished product. The finished product can be one or more cast films or sheets of the mixture of the invention, without any additional support or support, but it is more typical that the finished product is a laminate supported by other sheet material,

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for example through textile fibers, paper, cell material, Polyvinyl chloride sheet or film, or various combinations of such substrates, with or without the help of suitable adhesives are layered.

A construction that is suitable, for example, for clothing applications with a recommended thickness of 0.038 mm is, for example, has a textile base and a lower coating or a layer layer, which melamine resin and contains a relatively small amount of vinyl resin (B), and further has on the surface of such a layered layer outer layer or a sliding coating, which contains melamine resin and a relatively large amount of vinyl resin (B). A roughened fiber material can be used to make a wrinkled one To achieve appearance.

A construction similar to the one above and preferred for garments where optimal flexibility, soft texture and good draping are required, uses a slip coating that does not contain melamine resin and contains a relatively low proportion of vinyl resin (B).

Another preferred construction, for example for footwear in considerably greater thicknesses Order of magnitude of 0.508 mm is suitable, has a fibrous material base, a conventional, plasticized polyvinyl chloride layer on the fiber material, a conventional adhesive on the polyvinyl chloride layer, and finally an outer one

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skin covering, which is made from the composition according to the invention and contains a relatively high proportion of the vinyl resin (B) described.

The following examples, in which all quantitative data relate to weight, serve for further illustration of embodiments of the invention.

example 1

This example illustrates the preparation of a layered textile material.

The following slip coating or outer coating preparation is made:

Slip Coating Preparation I

Parts wet dry

Solution of thermoplastic

Polyurethane elastomer 4 3.6 8.7

Solution of hydroxyl-containing vinyl copolymer resin

Melamine resin

Silicone oil

Pigment concentrate

33.4 10.7 0.5 0.5 0.83 0.83 21.7 3.0

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The thermoplastic polyurethane elastomer can be of the polyester type (for example, reaction product of 1.4-butanediol adipic acid polyester with MDI, like this that commercial material is Estane 5,701; see also the above-mentioned article by Schollenberger). The solution to the Elastomers can contain 8.7 parts of the polymer dissolved in 17.45 parts of tetrahydrofuran and 17.45 parts of cyclohexanone, contain. The hydroxyl-containing copolymer resin can be the commercially available one Be a material known as VAGH which is calculated to be 91% vinyl chloride, 3% vinyl acetate and 5.7% hydroxyl than vinyl alcohol. 10.7 parts of the resin can be in 11.35 parts of tetrahydrofuran and 11.35 parts of cyclohexanone be dissolved. The melamine resin can be the commercially available material, which is known as cymel and which is ilexakis (methoxymethyl) melamine is. The silicone oil is a poly (dimethylsiloxane) commercially available as Union Carbide S-IO (specific weight 0.65; viscosity at 25 ° C, 1 to 2 centistokes). Its function is to help separate the layer from the release paper and to help create a desired viscosity in the coating solution.

The pigment concentrate can consist of 3.0 parts of pigment particles (for example 40% carbon black and 60% polyvinyl chloride), dissolved in 9.35 parts of tetrahydrofuran and 9.35 parts of cyclohexanone.

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On the surface of a continuous length of release paper, one brings a coating of the The above slip coating formulation is applied using a rotating gravure printing roll and the assembly is left pass through an oven which has a first zone heated to about 9 3 C and a subsequent zone heated to about 121 C Zone. The coated paper needs one Minute to go through the oven. The dry deposited film has a thickness of 0.0127 mm.

Prepare the following layer coating or lower coating preparation:

Layer coating preparation II

5 Parts dry 36 ate 2 5 25th 72 25th 3, 25th 10, 5 O, 0 ο, , 2 O, ο, 3, 6, 10

Estane 570! (Tetrahydrofuran
(ThF) -cyclohexanone solution)

¹¹ VAGH "(""")

"Cymel ⁿ resin

S-10 silicone

Pigment concentrate

Cyclohexanone

The above coating preparation, which creates a residual tackiness for good coating, is by means of a reversing roller at the rate of 27.1 g / m (dry) on the surface of the previously applied skin

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Cover pulled up. The assembly goes through an oven in two minutes, which is progressing has hotter zones at temperatures of 82, 93 and 121 ° C. Then another coating of the layering preparation is put through coating is applied by means of a reverse roll at a rate of 23.7 g / in (dry) and is pressed onto this deposit one layer of textile goods. The assembly goes through an oven in two minutes, which zones of 93, 121 and 1Λ9 C. Then the resulting, hardened laminate with the textile material support layer, which is firmly united with the layer layer, from the release paper stripped. The resulting finished synthetic leather sheet material is quite flexible, non-porous, and has a non-sticky surface which is quite hard, dry and is wear-resistant.

Example 2

This example illustrates the preparation of a product which can be used to manufacture footwear uppers suitable is.

The following skin covering preparation is prepared :

.1098 4 9 / 198-9

-αϊ-

Skin covering preparation · III

Parts

dry

Polyurethane (THF cyclohexanone

Solution) 52.5 10.5

Vinyl copolymer resin
(THF cyclohexanone
Solution)
Heiaminharz 30.1
1.05 • 9
1 , 6
, 05 silicone 3 3 Pigment concentrate
Cyclohexanone 4.0
20.25 1 , 85

The ingredients in the skin covering preparation are as described above. On a release paper reverse roll the skin coating formulation at a rate

pulled up from 27.1 g / m. The solvents are allowed to evaporate by turning the assembly within two minutes pass through an oven having zones heated to 82-93-121 ° C. Make the following adhesive preparation from:

Urethane Adhesive Preparation IV

Liquid polyester-polyurethane prepolymer 34.7

TDI -2.7

Methyl ethyl ketone 27.8

Cyclohexanone '34.8

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The polyurethane prepolymer used in the adhesive can be made from a polyester such as polyethylene adipate and TDI (see, for example, U.S. Patent 3,379,691) or an equivalent commercially available material such as Goodrich A-1060B be prepared. The adhesive has a lifespan of around eight hours in the container. The glue will be on the exposed Surface of the previously applied skin coating applied with a rotating pressure roller at a rate of

3.4 g / m. The assembly goes through an oven heated to 9-3121 ° C in one minute. One puts the following Low temperature footwear vinyl plastisol preparation:

Low temperature vinyl preparation for footwear V

Parts

Polyvinyl chloride resin powder

(Marvinol VR-50) "100

Dioctyl phthalate 25

Octyl decyl phthalate 33.4

Stabilizer (e.g. dibasic lead stearate) 2.0

Soot. 0.6 5

161.05

Two consecutive coats of the foregoing

Plastisols are applied to the adhesive coated surface

applied by means of tandem reverse rollers, whereby 441 g / m -

2 · 2

and applies 271 g / m coatings (total 712 g / m). Satin fabric is pressed onto the top of the plastisol. The order To fuse the plastisol, it is heated for two to three minutes at 149 C. The fabric is softened with the

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Polyvinyl chloride firmly combined and the latter firmly combined with the chewing cover over the interlayer Polyurethane adhesive. The resulting non-porous material for upper parts of footwear is flexible and has a permanent, non-adhesive, glossy leather surface, which created by the skin covering.

Example 3

This example illustrates a sheet material suitable for clothing that is highly flexible and has a Has the desired structure and desired draping. The material has a glossy surface with a soft feel.

The following slip coating formulation can be made:

Soft, non-glossy slip coating preparation VI

Parts wet dry

Lstane 5701 (solution in 50:50
Cyclohexanone tetrahydrofuran) 62 12.4

VAGh (solution in 50:50

Cyclohexanone tetrahydrofuran) 8.7 2.78

Syloid 73 silica gel (anhydrous

Silica in cyclohexanone) 22.5 3.5

Pigment concentrate 21.7 3.0

The silica gel acts as a lubricant. A mediated one

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Release paper can be used with the above preparation means

2 on a reverse roller at the rate of 30.5 g / m.

The coating can be cured in two minutes in a zoned oven at 82-93-121 ° C. The rest of the process can be the same as in Example 1 _s, ie the layer coating preparation II can be applied with a reversing roller at 23.7 g / m, the textile material pressed on, and the arrangement for two minutes in the oven divided into zones at 93-121- 1 ^ 9 ° C, after which the hardened laminate is stripped from the release paper. The laminate is notable for its good structure and draping (the melamine resin has been omitted from the slip coating), and yet it is sufficiently resistant to dry cleaning because the laminate coating contains the melamine resin.

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Claims (11)

Patent claims 1. Composition for producing a dry-cleanable synthetic leather sheet material, characterized in that it ate from a mixture of a thermoplastic polyurethane elastomer, one. Vinyl chloride-vinyl acetate-vinyl alcohol copolymer resin, and a hexakis (methoxymethyl) melamine resin or contains such a mixture. 2. Mass according to claim 1, characterized in that it is dissolved in an inert, volatile organic solvent. 3. Mass according to claim 1, characterized in that it is networked. * t. Mass according to claim 3, characterized in that it is in the form of a sheet, which is resistant to dry cleaning. 5. Use of the composition according to claim 1 to 4..for production a leather-like sheet material, consisting of a flexible carrier substrate, which with the Ilasse, in particular according to claim 3, is coated. 6. Use of the composition according to claim 1 to 4 for the production of a flexible, leather-like sheet material with a 109849/1989 212377? Structure and draping, which is suitable for clothing purposes is 3 wherein the sheet material is a slip coating layer a mass, which is a mixture of a thenrio] .- elastic Polyurethane elastomers and a vinyl chloro-vinyl acetate-vinyl alcohol copolymer resin comprises, and an underlying layer of a compound according to claim 3, uno consists of a load-bearing support layer made of textile goods, these layers being united with their surfaces lying on top of one another are. 7. Use according to claim 6, wherein the amounts of (A) thermoplastic polyurethane elastomer; and (B) vinyl chloride-vinyl acetate-vinyl alcohol copolymer resin in the underlying layer, 70 to 90 parts (A) and 10 to 2 5 parts (B) per 100 parts by weight of (A) plus (B). 8. Use according to claim 7, wherein the proportions of (A) and (B) are 75 to 85 parts of (A) and 15 to 25 parts of (B) per 100 parts by weight of (A) plus (B). 9, use of the composition according to claim 1 to 4 for the production of a leather-like or shiny leather-like sheet material, which is suitable for use as a material for footwear uppers, the material consisting of a liaut covering layer which is prepared from a composition according to claim 3, an underlying plasticized polyvinyl chloride resin layer which is adhered to the chewable coating layer, and of a 109849/1989
BATH ORIGINAL Support layer made of textile on this underlying layer consists, the layers with their superimposed Surfaces are united with each other. 10. Use according to claim 9, wherein the amounts of (A) thermoplastic polyurethane elastomer; and (B) vinyl chloride-vinyl acetate-vinyl alcohol copolymer resin in the ileal coating layer, 35 to 65 parts (A), and 35 to 65 parts (B) per 100 parts by weight of (A) plus (B). 11. Use according to claim 10, wherein the proportions of (A) and (B) 40 to 5 parts (A) and 45 to 60
Parts (B), and the amounts of Eexakis (methoxymethyl) melamine resin are from 0.5 to 10 parts per 100 parts by weight of (A) plus (B). 109849/1989